CN115010118B - Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof - Google Patents
Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 92
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000010426 asphalt Substances 0.000 claims abstract description 20
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
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- 229920000877 Melamine resin Polymers 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 7
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- 239000000463 material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910052786 argon Inorganic materials 0.000 description 4
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- 229920000767 polyaniline Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a method for preparing nitrogen-sulfur doped graded macroporous/mesoporous graphene by taking asphalt and petrochemical byproduct liquid heavy aromatic hydrocarbon as raw materials. The hierarchical macroporous/mesoporous graphene material is provided with a macroporous structure which is formed by mutually communicating graphene sheets, wherein macropores and mesoporous holes are formed in the graphene sheets; the nitrogen doping content of the hierarchical macroporous/mesoporous graphene material can be up to about 25%, and the sulfur doping content is about 1.0% under the condition that no additional sulfur source is added. When the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is applied to lithium ion batteries and sodium ion battery anode materials, the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is 1A g ‑1 The specific capacity can reach 1025.5mAh g when the current density is circulated to 500 circles and 1000 circles ‑1 (about 3 times the theoretical specific capacity of the graphite anode) and 256.5mAh g ‑1 Has good lithium and sodium storage performance.
Description
Technical Field
The invention belongs to the technical field of graphene preparation, and particularly relates to nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene, and a preparation method and application thereof.
Background
Graphene, as a typical two-dimensional material, tends to agglomerate during the preparation process due to pi-pi stacking, resulting in loss of its own unique properties. The two-dimensional graphene is constructed into a three-dimensional structure with good structure and interconnection, and the structure is provided with a macroporous/mesoporous structure, so that the characteristics of the layered structure of the graphene can be reserved, and the graphene has higher specific surface area and more ordered material energy transportation exchange, so that the graphene is endowed with multi-functionality. On the other hand, nitrogen and sulfur elements can improve the electronic structure of graphene after being doped into the graphene lattice due to multiple electrons outside the atomic nucleus, so that more excellent electrochemical performance is provided. Therefore, the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene has wide application prospects in the field of electrochemical energy storage.
However, due to crystallizationStructural inertness and sp of carbon lattices 2 The high covalent bond strength between hybridized carbon atoms makes the synthesis of such three-dimensional hierarchical porous graphene challenging. Currently, various synthetic methods have been reported, including Chemical Vapor Deposition (CVD), chemical activation, and the like. However, these methods, which are designed for specific applications, such as chemical methods, often suffer from problems such as chemical contamination or structural deterioration of graphene, and CVD methods generally require complicated steps and relatively high costs.
Asphalt is a low-value byproduct in the processing process of fossil fuel, contains rich polycyclic aromatic hydrocarbon, is easy to polymerize and aromatise in the heat treatment process, and the developed graphene material utilizing the characteristic is widely applied in the fields of energy storage, adsorption, catalysis and the like. However, due to the molten state and flowability of the pitch itself, the carbon atoms produced by its pyrolysis tend to produce large-sized aggregates. Meanwhile, it is difficult to controllably synthesize a three-dimensional graphene material having a hierarchical porous structure during carbonization because of the characteristics of pitch itself. Therefore, how to quickly prepare the nitrogen and sulfur doped graded macroporous/mesoporous graphene with low cost is a great challenge.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and the preparation method thereof aiming at the defects in the prior art. The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene has excellent lithium and sodium storage circulation and rate capability, and the preparation method is low in cost, does not need to add acid and alkali, strong oxidant, etchant and the like, and is easy to synthesize on a large scale.
The invention adopts the technical proposal for solving the problems that:
the nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is integrally in a cellular three-dimensional structure formed by stacking graphene sheets, wherein macropores and/or mesopores are distributed on the graphene sheets; the pore size of the macropores on the honeycomb three-dimensional structure is 0.5-5 microns; the size of macropores distributed on the graphene sheets is 50-100 nanometers, and the size of mesopores is 2-50 nanometers.
Press onAccording to the scheme, the specific surface area of the graded macroporous/mesoporous graphene is 120-400m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The content of nitrogen doping atoms in the hierarchical macroporous/mesoporous graphene is 12-25%, and the content of sulfur doping atoms is 0.4-1.5%.
The preparation method of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene comprises the following steps of:
1) After the asphalt is dispersed by liquid aromatic hydrocarbon in an ultrasonic way, adding a nitrogen source and alkali metal salt, grinding uniformly and drying; the melting temperature of the alkali metal salt is 600-1000 ℃;
2) And (3) calcining the product obtained in the step (1) in an air atmosphere, calcining in a protective atmosphere, washing and drying to obtain the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene.
According to the scheme, the asphalt is selected from one or more of petroleum asphalt, coal tar asphalt, mesophase asphalt and the like; the nitrogen source is one or more of melamine, urea, thiourea, polyaniline, phenylenediamine, dopamine and the like.
According to the scheme, the liquid aromatic hydrocarbon is one or a mixture of more of monocyclic aromatic hydrocarbon, bicyclic aromatic hydrocarbon and the like. Further, the monocyclic aromatic hydrocarbon is selected from one or a mixture of several of alkylbenzene, tetrahydronaphthalene, indane and the like; the double-ring arene is one or a mixture of more of naphthalene, acenaphthylene and the like.
According to the scheme, the liquid aromatic hydrocarbon can also adopt a byproduct heavy aromatic hydrocarbon mixture generated by petroleum catalytic cracking, and the components of the liquid aromatic hydrocarbon mixture comprise: the single-ring arene alkylbenzene, tetrahydronaphthalene, indane, indene, double-ring arene naphthalene, acenaphthylene, small amount of tricyclic arene and the like can be used for dispersing asphalt.
According to the above scheme, the alkali metal salt is selected from one or more of sodium chloride, potassium carbonate, lithium chloride and the like; wherein the mass fraction of sodium chloride is between 50 and 100 percent. To ensure proper melting temperature, it is necessary to ensure that the mass fraction of sodium chloride is not less than 50%.
According to the scheme, in the step 1), because the asphalt is in a flowing state, part of impurities and part of components are dissolved after liquid aromatic hydrocarbon is added, and the drying purpose is to evaporate the solvent so that the asphalt becomes a high-viscosity precursor. The drying conditions are generally oven drying at 70-90 ℃.
According to the scheme, in the step 1), the proportion relation between the asphalt mass and the liquid aromatic hydrocarbon volume is 1g: (10-30) mL; the mass ratio of the asphalt to the alkali metal salt is 1:10-1:100; the mass ratio of the nitrogen source to the asphalt is 1:10-1:1.
According to the scheme, in the step 2), the temperature is increased to 300-400 ℃ at the temperature rising rate of 1-5 ℃/min under the atmosphere, and the calcination time is 2-6 hours; under the protective atmosphere, the temperature is increased to 700-1100 ℃ at the heating rate of 1-5 ℃/min, and the calcination time is 2-8 hours. Wherein, during the calcining treatment in the protective atmosphere, one or more protective gases such as argon, nitrogen, hydrogen-argon mixture and the like are adopted.
The hierarchical macroporous/mesoporous graphene can be applied as a negative electrode material of a lithium ion battery and/or a sodium ion battery.
In the prior art, graphene is due to sp 2 The structure is stable, so that an additional etchant such as hydrogen peroxide is generally required for preparing the mesoporous graphene, thereby increasing the process complexity and environmental pollution. Compared with the prior art, the invention has the following beneficial effects:
firstly, preparing graphene by a solid-phase catalytic conversion method, and calcining in air by a two-step calcining technology to obtain a graphene precursor with rich pore channel structure so as to inhibit aggregation of the carbon precursor; and calcining in a protective atmosphere to realize atom directional rearrangement at high temperature, so as to obtain the high-quality sulfur-nitrogen doped hierarchical macroporous-mesoporous graphene. The invention can realize the construction of the macroporous-mesoporous structure without using strong acid and strong oxidant, thereby greatly reducing the industrial preparation cost of the hierarchical porous graphene and the dependence on expensive equipment, and being very potential to be applied to large-scale production.
Secondly, the invention removes low boiling point components in asphalt by utilizing liquid aromatic hydrocarbon separation, avoids using organic solvents such as toluene, carbon tetrachloride and the like, and reduces the cost; in addition, the raw materials take petrochemical byproduct asphalt as a carbon source, and the used liquid aromatic hydrocarbon can be directly replaced by petrochemical byproduct heavy aromatic hydrocarbon, so that the cost is low; moreover, the preparation process does not need to use acid and alkali, strong oxidant, etchant and the like.
Thirdly, the sulfur-nitrogen doped hierarchical macroporous-mesoporous graphene is used as a lithium ion and/or sodium ion battery cathode material, the three-dimensional network structure of the sulfur-nitrogen doped hierarchical macroporous-mesoporous graphene can provide a rapid transfer path for electrons, and the mesopores/macropores on the graphene nanosheets can provide excellent diffusion channels for ions, so that the diffusion paths of lithium ions and sodium ions are shortened, and the permeation of electrolyte is facilitated; in addition, the porous structure can effectively relieve structural stress generated when ions are repeatedly embedded into/extracted from the battery in the charging and discharging process, so that the structural integrity of the material is maintained.
Therefore, the method has the advantages of simple process, low cost, wide sources of raw materials, high three-dimensional degree of the graphene product, controllable nitrogen doping and the like, and has extremely high large-scale application potential.
Drawings
FIGS. 1 (a-b) are SEM images of hierarchical macroporous/mesoporous graphene synthesized in example 1; fig. 1 (c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in example 1.
FIG. 2 is a graph of nitrogen adsorption-desorption curves for the final samples obtained in examples 1-4.
FIG. 3 shows XRD patterns of final samples obtained in examples 1-4 and comparative examples 1, 2.
FIG. 4 is a Raman diagram of the final samples obtained in examples 1-4 and comparative examples 1, 2.
FIG. 5 (a) is a chart showing the charge-discharge cycle test of the lithium ion battery of the final sample obtained in examples 1 to 4; fig. 5 (b) is a lithium ion battery magnification test chart of the final samples obtained in examples 1 to 4.
FIG. 6 (a) is a graph showing the charge-discharge cycle test of the sodium ion battery of the final sample obtained in example 1; fig. 6 (b) is a sodium ion battery magnification test chart of the final sample obtained in example 1.
FIG. 7 (a-b) is an SEM image of nitrogen doped hierarchical macroporous/mesoporous graphene synthesized in comparative example 1; FIG. 7 (c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in comparative example 1.
FIG. 8 (a-b) is an SEM image of nitrogen doped hierarchical macroporous/mesoporous graphene synthesized in comparative example 2; FIG. 8 (c-d) is a TEM image of the hierarchical macroporous/mesoporous graphene synthesized in comparative example 2.
Fig. 9 (a) is a charge-discharge cycle test chart of a lithium ion battery of the final graphene sample obtained in comparative example 1-2; fig. 9 (b) is a lithium ion battery magnification test chart of the final sample obtained in comparative examples 1-2.
FIG. 10 (a) is a graph of sodium ion battery charge-discharge cycle test of the final graphene sample obtained in comparative examples 1-2; fig. 10 (b) is a sodium ion battery magnification test chart of the final sample obtained in comparative example-2.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the invention further, but are not to be construed as limiting the invention.
Example 1
A preparation method of macroporous/mesoporous graphene doped with nitrogen and sulfur comprises the following specific processes:
1) The liquid aromatic hydrocarbon in the embodiment is taken from a petrochemical refinery enterprise in China, and the specific components are as follows: monocyclic aromatic hydrocarbon (alkylbenzene (53.2%), indane or tetrahydronaphthalene (30.2%, indenes (5.3%)), bicyclic aromatic hydrocarbon (naphthalene (0.8%), acenaphthylene (3.1%), acenaphthylene (3.6%)) and other impurities (3.8%). 1g of petroleum asphalt is added with 10mL of the liquid aromatic hydrocarbon and then ultrasonically dispersed for 20min with 100w of ultrasonic power to obtain a mixture A;
then, uniformly mixing and grinding the mixture A with 20g of mixed salt of NaCl and KCl (the mass ratio of NaCl to KCl is 1:1) and 0.4g of melamine, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) Incubating mixture B in an air atmosphere at 360 ℃ for 4 hours, followed by slowly heating to 700 ℃ at a rate of 5 ℃/min in an argon atmosphere and incubating for 2 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene.
As shown in fig. 1, the microstructure of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene prepared in example 1 is a three-dimensional honeycomb structure formed by interconnected graphene sheets, and the pore size is 0.5-5 microns; from fig. 1b, it can be seen that the graphene sheets are thinner, and the nano-sheets have nano-holes with different sizes. The abundant macroporous/mesoporous structure on the graphene nanoplatelets can be clearly seen from TEM images, the mesoporous size is 2-50 nanometers, and the macroporous size is 50-100 nanometers (c-d in FIG. 1).
As can be seen from FIG. 2, the specific surface area of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene prepared in example 1 is 267m 2 g -1 The pore size distribution 15,22,35,50,73,94nm (Table 1) contained a mesoporous structure and a macroporous structure.
The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene obtained in example 1 has nitrogen atom and sulfur atom contents of 12.2% and 1.3%, respectively (table 2) detected by XPS.
The XRD patterns of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene obtained in example 1 are shown in fig. 3, and two broad peaks exist in the curves, which correspond to diffraction peaks of graphene on the (002) plane and the (100) plane respectively.
FIG. 4 is a Raman diagram of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene obtained in example 1, in which two graphene layers at 1330cm are observed -1 And 1591cm -1 Characteristic peaks in the vicinity, which correspond to lattice defects and sp of carbon atoms, respectively 2 In-plane stretching vibration of hybridized carbon atoms; in addition, at about 2800cm -1 The peak at represents the 2D peak of graphene, which occurs due to the effects of the vibrational behavior of the two phonon lattices.
Example 2
A preparation method of macroporous/mesoporous graphene doped with nitrogen and sulfur comprises the following specific processes:
1) Mixing alkylbenzene, tetrahydronaphthalene and acenaphthylene into 20mL according to the volume ratio of 1:1:1, adding 1g of petroleum asphalt, and then performing ultrasonic dispersion for 20min (ultrasonic power of 100 w) to obtain a mixture A;
then, uniformly mixing and grinding the mixture A with 20g of mixed salt of NaCl and KCl (the mass ratio of NaCl to KCl is 1:1) and 0.8g of melamine, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) Incubating mixture B in an air atmosphere at 380 ℃ for 4 hours, followed by an incubation in an argon atmosphere at a rate of 5 ℃/min to 800 ℃ for 2.5 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene.
Example 3
A preparation method of macroporous/mesoporous graphene doped with nitrogen and sulfur comprises the following specific processes:
1) Mixing alkylbenzene and indane into 15mL according to the same volume ratio of 1:1, adding 1g of petroleum asphalt, and then performing ultrasonic dispersion for 20min (the ultrasonic power is 100 w) to obtain a mixture A;
then, uniformly mixing and grinding the mixture A with 20g of mixed salt of NaCl and KCl (the mass ratio of NaCl to KCl is 1:1) and 1.0g of melamine, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) The mixture B was kept at 400℃for 4 hours in an air atmosphere, followed by a slow temperature increase to 800℃at a rate of 2℃per minute in an argon hydrogen atmosphere (wherein the volume fraction of hydrogen is 5%) and a 4 hour temperature hold; and cooling the product to room temperature, washing and drying to obtain the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene.
Example 4
A preparation method of macroporous/mesoporous graphene doped with nitrogen and sulfur comprises the following specific processes:
1) 1g of petroleum asphalt and 10mL of alkylbenzene are mixed and then are subjected to ultrasonic dispersion for 20min (the ultrasonic power is 100 w), so as to obtain a mixture A;
then, uniformly mixing and grinding the mixture A with 20g of mixed salt of NaCl and KCl (the mass ratio of NaCl to KCl is 1:1) and 2.0g of melamine, and drying at 80 ℃ to remove volatile substances to obtain a mixture B for later use;
2) Incubating mixture B in an air atmosphere at 400 ℃ for 4 hours, followed by an incubation at a rate of 3 ℃/min to 1100 ℃ in a nitrogen atmosphere for 2 hours; and cooling the product to room temperature, washing and drying to obtain the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene.
SEM, TEM, XRD and Raman of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene prepared in examples 2-4 are similar to those in example 1, except that specific surface areas of nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene samples obtained in different synthesis modes are different, pore size distribution is not completely the same, but common characteristics are that the samples all have a macroporous/mesoporous structure.
Comparative example 1
The only difference between comparative example 1 and example 1 is that: in step 1), melamine and other nitrogen sources are not added.
As can be seen from the SEM images of fig. 7 (a-b) and the TEM images of fig. 7 (c-d), comparative example 1 has a microstructure similar to that of example 1, and exhibits an integrated porous network structure, and has abundant mesopores on the surface and inside thereof.
In addition, XRD, BET and Raman spectra of the sample of comparative example 1 were also measured similarly to those of example 1, and are not listed here, except that XPS test showed only 1.6% of the nitrogen content of the product, with small amounts of nitrogen and sulfur originating from the raw materials, since no additional nitrogen source was added.
Comparative example 2
Comparative example 2 is different from example 1 in that: in step 1), melamine is not added; in step 2), mixture B was incubated at 360 ℃ for 4 hours in an argon atmosphere, then warmed to 700 ℃ at a rate of 5 ℃/min and incubated for 2 hours.
As can be seen from fig. 8 (a-b), comparative example 2 was not subjected to air atmosphere heat treatment, and the samples were stacked from irregular lamellar structure graphene, and had no apparent three-dimensional pore structure as a whole. This is consistent with what is observed in the TEM images of fig. 8 (c-d). From the nitrogen adsorption and desorption test, comparative example 2 has no obvious pore size distribution, which indicates that no macropores/mesopores exist in the prepared graphene sample (table 1).
Table 1 shows the specific surface area and pore size distribution data for examples 1-4 and comparative examples 1,2 (note: pore size in Table 1 is the pore size of macropores/mesopores on graphene nanoplatelets). Table 2 shows the sulfur and nitrogen atom content data in XPS for examples 1-4 and comparative examples 1, 2.
TABLE 1
TABLE 2
As can be seen from Table 2, as the amount of nitrogen source in examples 2 to 4 increases, it is demonstrated that the nitrogen doping concentration can be controlled by increasing the amount of nitrogen source.
Application: the materials of examples 1-4 were applied to Lithium Ion Battery (LIBs) and Sodium Ion Battery (SIBs) anode materials. The specific operation is as follows: the prepared graphene sample is used as an active substance, and is uniformly ground in a mortar in advance with a carbon black conductive agent and a PVDF adhesive according to the mass ratio of 7:2:1, and then NMP is added to continuously grind until uniform slurry is formed. The slurry was then knife coated onto copper foil and dried in a vacuum oven at 120 ℃ for 12 hours, then rolled and punched into round pole pieces of 12mm diameter. And weighing and recording the mass of each piece of pole piece in sequence, and multiplying the mass of the active substance, namely the mass difference between the pole piece mass and the blank copper foil wafer by the proportion of the active substance. In an argon-filled glove box (H) 2 O<0.1ppm，O 2 <0.1 ppm) was used for assembly of CR2025 coin cells. A Land CT2001A battery test system was used at 0.005-3V (vs. Li +/ Li) and 0.01-2.8V (vs. Na + Constant current charge and discharge test is carried out on the voltage window of/Na).
As shown in FIGS. 5 and 6, example 1 was used as LIBs and SIBs negative electrode at 1A g -1 Specific capacities of 1025.5mAh g when the current density is cycled to 500 circles and 1000 circles respectively -1 (about 3 times the theoretical specific capacity of the graphite anode) and 256.5mAh g -1 Has excellent lithium storage and sodium storage cycle and rate capability.
Fig. 9 and 10 are performance graphs of lithium ion batteries and sodium ion batteries of the final graphene samples obtained in comparative examples 1 and 2. Comparative example 1 negative to LIBsA pole having a specific capacity of 789.3mAh g when it is cycled to 500 turns -1 And at 5A g -1 The specific discharge capacity at a high current density was 315.6mAh g -1 . Comparative example 1 negative electrode for SIBs, 1A g -1 When the current density of (C) is cycled to 1000 circles, the specific discharge capacity is 219.2mAh g -1 . Comparative example 1 has better lithium and sodium storage cycle and rate performance than comparative example 2 because comparative example 1 has a hierarchical macroporous/mesoporous structure that facilitates ion and electron transfer. But still lower than example 1 for the following 2 points: firstly, the hierarchical porous structure graphene three-dimensional network structure can provide a rapid transfer path for electrons, and mesopores on the graphene nano-sheets can provide excellent diffusion channels for ions, so that the diffusion paths of lithium ions and sodium ions are shortened, and the permeation of electrolyte is facilitated; the porous structure can effectively relieve structural stress generated when ions are repeatedly embedded into/released from the battery in the charging and discharging process, so that the structural integrity of the material is maintained; on the other hand, nitrogen doping enhances the intrinsic conductivity of graphene, is more beneficial to electron transmission, and thus improves the energy storage performance.
The present invention can be realized by the respective raw materials listed in the present invention, and the upper and lower limits and interval values of the respective raw materials, and the upper and lower limits and interval values of the process parameters (such as temperature, time, etc.), and examples are not listed here.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (2)
1. The nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene is characterized in that the graphene is integrally in a honeycomb three-dimensional structure formed by stacking graphene sheets, and macropores and mesopores are distributed on the graphene sheets; the pore size of the macropores on the honeycomb three-dimensional structure is 0.5-5 microns; the size of macropores distributed on the graphene sheets is 50-100 nanometers, and the size of mesopores is 2-50 nanometers;
the specific surface area of the graded macroporous/mesoporous graphene is 120-400m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The content of nitrogen doping atoms in the hierarchical macroporous/mesoporous graphene is 12-25%, and the content of sulfur doping atoms is 0.4-1.5%;
the preparation method of the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene is characterized by comprising the following steps of:
1) Adding 10mL of liquid aromatic hydrocarbon into 1g of petroleum asphalt, and performing ultrasonic dispersion for 20min with 100w ultrasonic power to obtain a mixture A; then the mixture A is uniformly mixed and grinded with 20g of NaCl and KCl mixed salt and 0.4g of melamine, and volatile substances are removed by drying at 80 ℃ to obtain a mixture B; wherein the mass ratio of NaCl to KCl in the NaCl and KCl mixed salt is 1:1;
2) Incubating mixture B in an air atmosphere at 360 ℃ for 4 hours, followed by slowly heating to 700 ℃ at a rate of 5 ℃/min in an argon atmosphere and incubating for 2 hours; after the product is cooled to room temperature, washing and drying are carried out, and then the nitrogen-sulfur doped hierarchical macroporous/mesoporous graphene is obtained;
the specific components of the liquid aromatic hydrocarbon are as follows: 53.2% of alkylbenzene, 30.2% of indane or tetrahydronaphthalene, 5.3% of indene, 0.8% of naphthalene, 3.1% of acenaphthylene, 3.6% of acenaphthylene, 3.8% of impurities and the sum of the components is 100%.
2. Use of the hierarchical macroporous/mesoporous graphene of claim 1 as a negative electrode material for lithium ion batteries and/or sodium ion batteries.
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